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Inorganics
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Fifth Element: The Current State of Boron Chemistry
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Fifth Element: The Current State of Boron Chemistry

A special issue of Inorganics (ISSN 2304-6740).

Deadline for manuscript submissions: closed (31 March 2023) | Viewed by 26793

Special Issue Editor

Dr. Marina Y. Stogniy

E-Mail Website
Guest Editor
A.N. Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences, 119991 Moscow, Russia
Interests: polyhedral boron compounds; carboranes; metal complexes; catalysis; synthesis, structure
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Boron chemistry is one of the most diverse and rapidly developing fields of modern chemistry. This is primarily due to the wide variety of compounds that boron is capable of forming, ranging from simple inorganic compounds such as oxides, nitrides and halides to organoboron compounds that play a huge role in organic synthesis, as well as unusual cluster structures in which an atypical electron-deficient bond is realized. Another reason is the wide variety of applications of boron and boron-containing compounds, including polymers, ceramics, heat-resistant materials, semiconductors, synthesis of organic fine chemicals, pharmaceuticals, medicines etc.

This Special Issue aims to collect data on the latest advances in synthetic and applied boron chemistry. We invite the submission of high-quality research on the synthesis, characterization, physical and chemical properties, reaction mechanisms as well as theoretical aspects and practical application of all types of boron compounds, including organoboron compounds, metal complexes with boron-based ligands and polyhedral boron clusters.

We are pleased to invite all researchers who are working in the area of boron chemistry to submit a manuscript to this Special Issue as an original research paper, communication or review.

Dr. Marina Yu. Stogniy
Guest Editor

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Inorganics is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • boron compounds
  • synthesis
  • structure
  • properties
  • fundamentals
  • applications

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Related Special Issue

Published Papers (13 papers)

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Editorial

Jump to: Research, Review, Other

4 pages, 190 KiB  
Editorial
Fifth Element: The Current State of Boron Chemistry
by Marina Yu. Stogniy
Inorganics 2024, 12(1), 10; https://doi.org/10.3390/inorganics12010010 - 25 Dec 2023
Viewed by 2008
Abstract
The fifth element of the Periodic Table is boron [...] Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)

Research

Jump to: Editorial, Review, Other

12 pages, 3916 KiB  
Article
Synthesis, Structure and Bonding of the Tungstaboranes [Cp*W(CO)2B3H8] and [(Cp*W)3(CO)2B4H7]
by Stutee Mohapatra, Sourav Gayen, Sampad Shyamal, Jean-François Halet and Sundargopal Ghosh
Inorganics 2023, 11(6), 248; https://doi.org/10.3390/inorganics11060248 - 7 Jun 2023
Cited by 2 | Viewed by 1563
Abstract
The structure and bonding of two novel tungstaboranes which were synthesized using diverse synthetic methods are described. (i) The room-temperature photolysis of [Cp*W(CO)3Me] with [BH3·SMe2] led to the isolation of the hydrogen-rich tungstaborane [Cp*W(CO)2B3 [...] Read more.
The structure and bonding of two novel tungstaboranes which were synthesized using diverse synthetic methods are described. (i) The room-temperature photolysis of [Cp*W(CO)3Me] with [BH3·SMe2] led to the isolation of the hydrogen-rich tungstaborane [Cp*W(CO)2B3H8] (1). Its geometry consists of an arachno butterfly core similar to tetraborane(10) and obeys the Wade-Mingos electron counting rules (n vertices, n + 3 skeletal electron pairs (seps)). (ii) Further, the tungstaborane [(Cp*W)3(μ-H)2(μ3-H)(μ-CO)2B4H4] (4) was isolated by thermolysis reaction of a tungsten intermediate, obtained by low temperature reaction of [Cp*WCl4] and [LiBH4·THF] with [Cr(CO)5·THF]. Compound 4 which seems to have formed by replacement of a BH unit in [(Cp*W)2B5H9] by the isoelectronic fragment {Cp*W(CO)2}, adopts an oblato-nido hexagonal-bipyramidal core (n vertices, n–1 seps). Both compounds were characterized using multinuclear NMR, IR spectroscopy, mass spectrometry as well as single crystal X-ray diffraction analysis. In addition, density functional theory (DFT) calculations were performed in order to elucidate their bonding and electronic structures. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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13 pages, 1347 KiB  
Article
Design and Synthesis of New Boron-Based Benzo[c][1,2,5]oxadiazoles and Benzo[c][1,2,5]thiadiazoles as Potential Hypoxia Inhibitors
by Sasmita Das, Mohammed Adil Shareef and Bhaskar C. Das
Inorganics 2023, 11(1), 34; https://doi.org/10.3390/inorganics11010034 - 9 Jan 2023
Cited by 2 | Viewed by 2007
Abstract
Benzo[c][1,2,5]oxadiazoles and benzo[c][1,2,5]thiadiazoles are recognized to possess potent pharmacological activities including anticancer potential. In continuation of our research endeavors in the development of boron-based heterocycles as potential therapeutic agents, herein we report the design and synthesis of new series of boron-based benzo[c][1,2,5]oxadiazoles and [...] Read more.
Benzo[c][1,2,5]oxadiazoles and benzo[c][1,2,5]thiadiazoles are recognized to possess potent pharmacological activities including anticancer potential. In continuation of our research endeavors in the development of boron-based heterocycles as potential therapeutic agents, herein we report the design and synthesis of new series of boron-based benzo[c][1,2,5]oxadiazoles and benzo[c][1,2,5]thiadiazoles as anticancer agents targeting tumor hypoxia. A series of seventeen compounds were synthesized in two steps in an efficient manner via substitution reactions followed by subsequent hydrolysis of aryltrifluoroboronate salts into corresponding boronic acid derivatives in the presence of silica. This is the first example to develop boron-based hypoxia agents. The synthesized hybrids were characterized by suitable spectroscopic techniques. The biological studies are currently underway. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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13 pages, 5210 KiB  
Article
A New Approach for the Synthesis of Powder Zinc Oxide and Zinc Borates with Desired Properties
by Irina V. Kozerozhets, Varvara V. Avdeeva, Grigorii A. Buzanov, Evgeniy A. Semenov, Yulia V. Ioni and Sergey P. Gubin
Inorganics 2022, 10(11), 212; https://doi.org/10.3390/inorganics10110212 - 17 Nov 2022
Cited by 12 | Viewed by 2102
Abstract
Zinc borates are widely used in industry due to their thermal stability as a flame retardant in the production of plastics, rubber, and other polymer compositions. We have developed a simple and effective approach for the synthesis of zinc borate powders with desired [...] Read more.
Zinc borates are widely used in industry due to their thermal stability as a flame retardant in the production of plastics, rubber, and other polymer compositions. We have developed a simple and effective approach for the synthesis of zinc borate powders with desired properties, including desired particle size, low bulk density, high reactivity, etc. Zinc borates were prepared by the thermal treatment of a concentrated water–carbohydrate solution of a zinc salt until finely dispersed ZnO was formed, followed by its hydrothermal treatment at 90–300 °C as part of a suspension based on a hot aqueous solution of H3BO3. According to X-ray powder diffraction, IR spectroscopy, and TG–DSC data, depending on the temperature of hydrothermal treatment, a decrease in the water content in the structure of synthesized zinc borate particles is observed. TEM and SEM data indicate the formation of isometrically shaped zinc borate particles in the nanometer range during hydrothermal treatment above 250 °C. Varying the temperature of the hydrothermal treatment affects the average size and fineness of the structure of the zinc borate particles. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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14 pages, 3384 KiB  
Article
How to Protect ortho-Carborane from Decapitation—Practical Synthesis of 3,6-Dihalogen Derivatives 3,6-X2-1,2-C2B10H10 (X = Cl, Br, I)
by Akim V. Shmal’ko, Sergey A. Anufriev, Kyrill Yu. Suponitsky and Igor B. Sivaev
Inorganics 2022, 10(11), 207; https://doi.org/10.3390/inorganics10110207 - 13 Nov 2022
Cited by 3 | Viewed by 1824
Abstract
The 3-halogen and 3,6-dihalogen derivatives of ortho-carborane 3-X-1,2-C2B10H11 and 3,6-X2-1,2-C2B10H10 (X = Cl, Br, I) were prepared by Cu-assisted halodeboronation of the corresponding pinacolborate derivatives 3-Bpin-1,2-C2B10H [...] Read more.
The 3-halogen and 3,6-dihalogen derivatives of ortho-carborane 3-X-1,2-C2B10H11 and 3,6-X2-1,2-C2B10H10 (X = Cl, Br, I) were prepared by Cu-assisted halodeboronation of the corresponding pinacolborate derivatives 3-Bpin-1,2-C2B10H11 and 3,6-(Bpin)2-1,2-C2B10H10. It was shown that decapitation of 3-Cl-1,2-C2B10H11, similarly to the corresponding bromo and iodo derivatives, proceeds regioselectively with the retention of the B-Cl bond. Crystal structures of 3,6-Cl2-1,2-C2B10H10 and Cs [3-Cl-7,8-C2B9H11] were determined by single crystal X-ray diffraction. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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17 pages, 3372 KiB  
Article
12-Vertex closo-3,1,2-Ruthenadicarbadodecaboranes with Chelate POP-Ligands: Synthesis, X-ray Study and Electrochemical Properties
by Anastasiya M. Zimina, Nikolay V. Somov, Yulia B. Malysheva, Nadezhda A. Knyazeva, Alexander V. Piskunov and Ivan D. Grishin
Inorganics 2022, 10(11), 206; https://doi.org/10.3390/inorganics10110206 - 11 Nov 2022
Cited by 3 | Viewed by 1596
Abstract
A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ2- or κ3-binding modes. Such κ2–κ3 [...] Read more.
A class of so-called POP ligands (Xanthos, NiXantphos, DPEphos) are of a great interest to the coordination chemistry due to their wide P-M-P bite angles and ability to show either κ2- or κ3-binding modes. Such κ2–κ3-rearrangement is valuable for catalytic application and internal stabilization of intermediates. To widen the scope of ruthenium-based catalysts for Atom Transfer Radical Polymerization (ATRP) two new approaches to the synthesis of closo-ruthenacarboranes with aforementioned POP ligands were developed and six new 17-e (3,3-(POP)-3-Cl-closo-3,1,2-RuC2B9H11; 2, 4, 7) and 18-e (3,3-(POP)-3-NCCH3-closo-3,1,2-RuC2B9H11; 3, 5, 8) clusters were synthesized and characterized by means of NMR or ESR spectroscopy, MALDI mass-spectrometry and single crystal X-ray diffraction studies. The unique 18-e complex of Ru(II) with dioxygen ligand 3,3-(DPEphos)-3-(η2-O2)-closo-3,1,2-RuC2B9H11 (9) was isolated and characterized by X-ray diffraction. It was shown that aforementioned POP ligands coordinate to ruthenium by two phosphorus atoms in a κ2-fashion. The performed electrochemical studies have shown reversible Ru(II)-Ru(III) transition making the complexes suitable for application in catalysis of polymerization. The test experiments on methyl methacrylate (MMA) polymerization indicate the proceeding of the process in according with an ATRP mechanism. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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13 pages, 2564 KiB  
Article
New Aspects of the Synthesis of closo-Dodecaborate Nitrilium Derivatives [B12H11NCR]− (R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7): Experimental and Theoretical Studies
by Alexey V. Nelyubin, Ilya N. Klyukin, Alexander S. Novikov, Andrey P. Zhdanov, Nikita A. Selivanov, Alexander Yu. Bykov, Alexey S. Kubasov, Konstantin Yu. Zhizhin and Nikolay T. Kuznetsov
Inorganics 2022, 10(11), 196; https://doi.org/10.3390/inorganics10110196 - 2 Nov 2022
Cited by 10 | Viewed by 1830
Abstract
The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B12H11NCR]−, R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7 is [...] Read more.
The preparation of novel nitrilium derivatives of closo-dodecaborate anion [B12H11NCR]−, R = n-C3H7, i-C3H7, 4-C6H4CH3, 1-C10H7 is described. Target compounds were obtained in good yields (up to 73%). The synthesis of target borylated nitrilium derivatives was characterised by the simplicity of the chemical apparatus and the absence of the necessity for the purification of desired compounds. The crystal structures of previously obtained [B12H11NCCH3]− and novel [B12H11NCC3H7]− were established with the help of X-ray structure analysis. DFT-analysis of several nitrilium derivatives [B12H11NCR]−, R = CH3, C3H7, 4-CH3C6H4 was carried out. The main peculiarities of the C≡N bond of the exo-polyhedral substituent were revealed in terms of bond lengths, bond orders and atomic charges. The LUMO orbitals of the systems considered were examined for understanding of the electrophilic nature of the nitrilium derivatives of the closo-dodecaborate anion. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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14 pages, 4920 KiB  
Article
Theoretical Insight into B–C Chemical Bonding in Closo-Borate [BnHn−1CH3]2− (n = 6, 10, 12) and Monocarborane [CBnHnCH3]− (n = 5, 9, 11) Anions
by Ilya N. Klyukin, Anastasia V. Kolbunova, Alexander S. Novikov, Andrey P. Zhdanov, Konstantin Yu. Zhizhin and Nikolay T. Kuznetsov
Inorganics 2022, 10(11), 186; https://doi.org/10.3390/inorganics10110186 - 28 Oct 2022
Cited by 2 | Viewed by 1603
Abstract
A theoretical investigation of mono-methyl derivatives of closo-borate anions of the general form [BnHnCH3]2– (n = 6, 10, 12) and monocarboranes [HCBnHnCH3]− (n = 5, 9, 11) was [...] Read more.
A theoretical investigation of mono-methyl derivatives of closo-borate anions of the general form [BnHnCH3]2– (n = 6, 10, 12) and monocarboranes [HCBnHnCH3]− (n = 5, 9, 11) was carried out. An analysis of the main bonding descriptors of exo-polyhedral B–C bonds was performed using the QTAIM (quantum theory of “Atoms in Molecules”), ELF (electron localisation function), NBOs (natural bond orbitals) analyses and several other approaches for the estimation of B–C bond orders (viz. Laplacian bond order (LBO), fuzzy bond order (FBO) and Mayer and Wiberg formalisms). Based on the data obtained on electron density descriptors, it can be concluded that orbital interaction increases with increasing boron cluster size. The present investigation provides a better understanding of exo-polyhedral B–C bond phenomena in boron cluster systems. The data obtained can be used to estimate B–C bond strength, which can be useful for studies devoted to the synthesis and properties of boron cluster systems. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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12 pages, 1563 KiB  
Article
New Aspects of Ruthenium-Mediated Polyhedral Contraction of Monocarbollides
by Dmitry A. Loginov, Fedor M. Dolgushin, Vitalii E. Konoplev and Maxim V. Tachaev
Inorganics 2022, 10(10), 158; https://doi.org/10.3390/inorganics10100158 - 28 Sep 2022
Viewed by 1604
Abstract
It has been shown that the interaction of tris(triphenylphosphine)ruthenium dichloride RuCl2(PPh3)3 (1) with 10-vertex monocarborane [6-Ph-nido-6-CB9H11]−[Et4N]+ (2) under mild thermolysis conditions is not [...] Read more.
It has been shown that the interaction of tris(triphenylphosphine)ruthenium dichloride RuCl2(PPh3)3 (1) with 10-vertex monocarborane [6-Ph-nido-6-CB9H11]−[Et4N]+ (2) under mild thermolysis conditions is not selective due to the undesired coordination of ruthenium to a phenyl substituent in the carborane and phosphine ligands, giving the series of new classical and non-classical metallacarborane complexes. In contrast, the reaction of 1 and monocarborane [arachno-6-CB9H14]−[Et4N]+ (3) proceeds more selectively with the formation of the only one product, a isocloso-structured metallacarborane. The structures of two ruthenacarboranes were resolved by X-ray diffraction. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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13 pages, 3637 KiB  
Article
Nucleophilic Substitution at a Coordinatively Saturated Five-Membered NHC∙Haloborane Centre
by Gargi Kundu, Srinu Tothadi and Sakya S. Sen
Inorganics 2022, 10(7), 97; https://doi.org/10.3390/inorganics10070097 - 7 Jul 2022
Cited by 5 | Viewed by 2495
Abstract
In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl2 yields [...] Read more.
In this paper, we have used a saturated five-membered N-Heterocyclic carbene (5SIDipp = 1,3-bis-(2,6-diisopropylphenyl)imidazolin-2-ylidine) for the synthesis of SNHC-haloboranes adducts and their further nucleophilic substitutions to put unusual functional groups at the central boron atom. The reaction of 5-SIDipp with RBCl2 yields Lewis-base adducts, 5-SIDipp·RBCl2 [R = H (1), Ph (2)]. The hydrolysis of 1 gives the NHC stabilized boric acid, 5-SIDipp·B(OH)3 (3), selectively. Replacement of chlorine atoms from 1 and 2 with one equivalent of AgOTf led to the formation of 5-SIDipp·HBCl(OTf) (4) and 5-SIDipp·PhBCl(OTf) (5a), where all the substituents on the boron atoms are different. The addition of two equivalents of AgNO3 to 2 leads to the formation of rare di-nitro substituted 5-SIDipp·BPh(NO3)2 (6). Further, the reaction of 5-SIDipp with B(C6F5)3 in tetrahydrofuran and diethyl ether shows a frustrated Lewis pair type small molecule activated products, 7 and 8. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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Review

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63 pages, 38378 KiB  
Review
Charge-Compensated Derivatives of Nido-Carborane
by Marina Yu. Stogniy, Sergey A. Anufriev and Igor B. Sivaev
Inorganics 2023, 11(2), 72; https://doi.org/10.3390/inorganics11020072 - 2 Feb 2023
Cited by 11 | Viewed by 2213
Abstract
This review summarizes data on the main types of charge-compensated nido-carborane derivatives. Compared with organic analogs, onium derivatives of nido-carborane have increased stability due to the stabilizing electron-donor action of the boron cage. Charge-compensated derivatives are considered according to the type of heteroatom [...] Read more.
This review summarizes data on the main types of charge-compensated nido-carborane derivatives. Compared with organic analogs, onium derivatives of nido-carborane have increased stability due to the stabilizing electron-donor action of the boron cage. Charge-compensated derivatives are considered according to the type of heteroatom bonded to a boron atom. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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36 pages, 10007 KiB  
Review
Effect of Nature of Substituents on Coordination Properties of Mono- and Disubstituted Derivatives of Boron Cluster Anions [BnHn]2– (n = 10, 12) and Carboranes with exo-Polyhedral B–X Bonds (X = N, O, S, Hal)
by Evgenii Yu. Matveev, Varvara V. Avdeeva, Konstantin Yu. Zhizhin, Elena A. Malinina and Nikolay T. Kuznetsov
Inorganics 2022, 10(12), 238; https://doi.org/10.3390/inorganics10120238 - 2 Dec 2022
Cited by 31 | Viewed by 2473
Abstract
This review systematizes data on the coordination ability of mono- and disubstituted derivatives of boron cluster anions and carboranes in complexation with transition metals. Boron clusters anions [BnHn]2–, monocarborane anions [CBnHn–1]– [...] Read more.
This review systematizes data on the coordination ability of mono- and disubstituted derivatives of boron cluster anions and carboranes in complexation with transition metals. Boron clusters anions [BnHn]2–, monocarborane anions [CBnHn–1]–, and dicarboranes [C2BnHn–2] (with non-functionalized carbon atoms) (n = 10, 12) containing the B–X exo-polyhedral bonds (X = N, O, S, Hal) are discussed. Synthesis and structural features of complexes known to date are described. The effect of complexing metal and substituent attached to the boron cage on the composition and structures of the final complexes is analyzed. It has been established that substituted derivatives of boron cluster anions and carboranes can act as both ligands and counterions. A complexing agent can coordinate substituted derivatives of the boron cluster anions due to three-center two-electron 3c2e MHB bonds, by the substituent functional groups, or a mixed type of coordination can be realized, through the BH groups of the boron cage and the substituent. As for B-substituted carboranes, complexes with coordinated substituents or salts with non-coordinated carborane derivatives have been isolated; compounds with MHB bonding are not characteristic of carboranes. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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Other

8 pages, 604 KiB  
Concept Paper
Gold(III) Complexation in the Presence of the Macropolyhedral Hydridoborate Cluster [B20H18]2−
by Varvara V. Avdeeva, Anna V. Vologzhanina, Alexey S. Kubasov, Nailya S. Akhmadullina, Oleg N. Shishilov, Elena A. Malinina and Nikolay T. Kuznetsov
Inorganics 2022, 10(7), 99; https://doi.org/10.3390/inorganics10070099 - 10 Jul 2022
Cited by 9 | Viewed by 1892
Abstract
Gold(III) complexation with the octadecahydrido-eicosaborate anion [B20H18]2− was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl2]BF4 (L = bipy, phen) reacted with [B20H18]2−, complexes [...] Read more.
Gold(III) complexation with the octadecahydrido-eicosaborate anion [B20H18]2− was studied for the first time. It was found that when gold(III) complexes [Au(L)Cl2]BF4 (L = bipy, phen) reacted with [B20H18]2−, complexes [Au(L)Cl2]2[B20H18] were isolated. The compounds consisted of a cationic gold(III) complex [Au(L)Cl2]+ and the hydridoborate cluster as a counterion. X-ray diffraction studies revealed weak B–H...Au interactions for both compounds. Note that more reactive anions [BnHn]2− (n = 10, 12) in similar reactions with gold(III) complexes resulted in gold mirror reactions. Full article
(This article belongs to the Special Issue Fifth Element: The Current State of Boron Chemistry)
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